Bis-p-dithiino(2,3-e: 2{40 ,3{40 -g) (2,1,3)benzothiadiazole-5,6,9,10-tetracarbonitrile

ABSTRACT

Novel polycyanodithiino aromatic N-heterocyclic compounds are prepared. These are useful as fungicides and bactericides.

United States Patent [191 Kurihara et al.

[ BIS-P-DlTHIINO(2,3-E: 2',3-G)

(2,1,3)BENZOTHIADIAZOLE-S,6,9,l0- TETRACARBONITRILE [75] Inventors: Norman H. Kurihara, Walnut Creek; Donald E. Bublitz, Concord,

both of Calif.

[73] Assignee: The Dow Chemical Company,

Midland, Mich.

[22] Filed: Feb. 20, 1973 [21] App]. No.: 333,942

Related U.S. Application Data [62] Division of Ser; No. 104,799, Jan. 7, 1971, Pat. No.

[52] U.S. Cl. 260/304 Dec. 10, 1974 Primary ExaminerRichard J. Gallagher Attorney, Agent, or Firm-S. Preston Jones [57] ABSTRACT Novel polycyanodithiino aromatic N-heterocyclic compounds are prepared. These are useful as fungicides and bactericides 1 Claim, No- Drawings 1 BIS-P-DITHIINO(2,3-E: 2',3 -G) BENZ9TH AD AZQ E:

TETRACARBONITRILE This is a division of application Ser. No. 104,799, filed Jan. 7, 1971, now US. Pat. No. 3,761,475.

SUMMARY OF THE INVENTION This invention is directed to polycyanodithiino aromatic N-heterocyclic compounds corresponding to the formula In this and succeeding formulae, R represents 2,3-pyrazinediyl 5,6-dichloro-2,jpyraiinediyl 3,6-dichloro 4,ipyridazinediyl 6-chloro-3,4-pyridazinediyl N H i 5,6,7,8-tetrachloro 2,3-ouinoxalinediyl 2,3-dicyano-[p-dithiino(2,3 b )pyrazine-6,7-diyl] NC S will) dichloro-cyano-pyridinediyl.

Cl: CN

2,3,8-tricyano-[p-dithiino( 2,3-b)pyridine6,7-diyl] izior 5,6-dicyano-[p-dithiino(2,3-e)-2,1,3-benzothiadiazole- 8,9-diyl] 6,7 dibromo-2,l,3-benzothiadiazole-4,5-diyl 2,1 ,3-benzothiadiazole-5 ,6-diyl X Na S C-- 0 N solvent ON 2 NaX A CN -CN s wherein R is as hereinbefore defined and X is chloro or bromo.

In carrying out the reaction, the haldaromatic com- I pound starting material is dissolved in a solvent such as,

for example, dimethylforrnamide, acetone, N- methylpyrrolidone or dimethylacetamide. To this mixture is thereafter added the disodium-cis-l,2-dicyano- 1,2-ethylene dithiolate. The reactants are maintained under agitation during the reaction period. The reaction is carried out at temperatures between about 25 and about 100 C. and depending upon the specific reactants and solvent employed, the reaction is usually complete in from about 8 to about hours. Upon completion of the reaction, the reaction mixture is poured into cold ,water or poured over ice and the crude solid product which precipitates is recovered by filtration or other conventional separatory procedures. The product can then be purified by conventional tech niqu es such as, for example, elution on a silica gel col- 3 umn with a solvent such as chloroform, extraction with a solvent such as chloroform followed by crystallization from a mixture of ethyl acetate and acetone or other well known purification procedures.

DESCRIPTION-OF SOME PREFERRED EMBODIMENTS EXAMPLE I I p- Dithiino(2,3-b)pyrazine-2,3-dicarbonitrile A solution is prepared containing 3.7 grams of disodium-cis-1,2-dicya.no-l ,Z-ethylene dithiolate dissolved in 35 milliliters of dry dimethylformamide and maintained under agitation. To this agitated solution is added a solution containing-3l0 grams of 2,3-dichloropyrazine in 35 milliliters of dry dimethylformamide. The mixture was maintained overnight (about 14 hours) under agitation at 50 C and thereafter poured into ice water. The crude solid p-dithiino( 2,3-b)pyrazine- 2,3dicarbonitrile product which precipitated was recovered by filtration and dried. The solid product was thereafter eluted with chloroform on a silica gel column..The product was recovered in a yield of 23,percent of theoretical and melted at l63".l65 C. Upon analysis, the product was found to have'carbon, hydrogen and nitrogen contentsof 43.9, 0.8 and 25.8 percent, respectively, as compared with the theoretical contents of 44.0, 0.9 and 25.6 percent, respectively, calculated for the above-named structure.

1 A EXAMPLE ll '3 6,7-Dichloro-p-dithiino(2,3-b)pyrazine-2,3-

dicarbon'itrile' I p To an agitated solution of NJ grams of tetra- EXAMPLE m 4,5-Dibromo-p-dithiino(2,3-

e 2, l ,3 )benzothiadiazole-7,8-dicarbonitrile .dithiino( 2,3-e:2',3 '-g)(2,1,3 )benzothiadiazol-S ,6,9, l 0- tetracarbonitrile corresponding to the formula (3N cN| S I s TON T Ii S/ CN s N The structure of each compound was confirmed by its mass spectrum.

The following compounds of the present invention are prepared in accordance with methods herein set forth:

6,7,8,Q-Tetrachloro-p-dithiino(2,3-b)quinoxaline- 2,3-dicarbonitrile N s or- ION 01 CN melting at 276-279 C., with decomposition, prepared chloropyrazine dissolved in 50 milliliters of dry dimethylformamide was added a solution of 10.0 grains of disodium-l ,2-dicyano-l ,2-ethylene dithiolate dissolved in 100 milliliters of dry dimethylformamide. The temperature of the mixture rose to C. and then dropped to room temperature. The mixture was maintained under ered by suction filtration, dried and purified by elution was chloroform on a silica gel column. The product was recovered in a yield of 45 percent of theoretical and melted at 184 C. Upon analysis by mass spectrometry,

by the reaction of 2,3,5,6,7,8-hexachloroquinoxaline and disodium-cisl ,Z-dicyano- 1 ,Z-ethylene dithiolate in dimethylformarnide.

Bis?p-dithiino( 2,3 -b:2 ',3 '-e )pyrazine 2,3 ,7 ,8-

tetracarbonitrile melting at 280 C., with decomposition, prepared by the reaction of tetrachlor'opyrazine with disodium-cisl,Z-dicyano-l,Z-ethylenedithiolate in dimethylformamide.

the product was found to have a molecular weight of r 286, based on chlorine having an atomic weight of 35.

p-Dithiino(2,3-f)(2, l ,3 )benzothiadiazole-6,7-

dicarbonitrile a .ethylenedithiolate in dimethylformamide at 40 C. for

24 hours.

A mixture of 6,8-dichloro-p-dithiino(2,3-b)pyridine- 2,3,7-tricarbonitrile and 5,7-dichloro-p-dithiino(2,3- c)pyridine-2,3,S-tricarbonitrile melting at l60200 C. and prepared by the reaction of tetrachloro-3- cyanopyridine and disodium-cis-l ,2-dicyano-l ,2- ethylenedithiolate in dimethylformamide.

Bis-p-dithiino-(2,3-b:2,3'-e)pyridine-2,3,7,8,10-

pentacarbonitrile melting at 29 8-300 C. and prepared by the reaction of tetrachloro-4-cyanopyridine and disodium-l ,2-

dicyano-l ,2-ethylenedithiolate in dimethylformamide at room temperature for 60 hours.

3-Chloro-p-dithiino-(2,3-c)pyridazine-6,7-

dicarbonitrile o1-K S\CN melting at 145 C., with decomposition, and prepared by the reaction of 3,4,6-trichloropyridazine with disodium-cisl ,2-dicyano-l ,2-ethylenedithiolate in dimethylformamide.

5 ,8 -Dichloro-p-dithiino( 2,3-d)pyridazine-2,3-

dicarbonitrile s CN melting at 263-265 C., with decomposition, and prepared by the reaction of tetrachloropyridazine and disodium-cis-l ,2-dicyanol ,Z-ethylenedithiolate in dimethyl-formamide.

In accordance with the present invention, it has been discovered that the dithiino compounds can be em,- ployed for the control of many bacterial and fungal ormany growing plants to control leaf-attaching fungal organisms or dispersed in soil or applied to plant seeds to control the root and seed attacking organisms of mold and damping off. In still other operations they can be applied to orchard floor surfaces to control overwintering spores of many fungal organisms. In still further operations, the compounds of the invention or compositions containing them as toxic constituents can be included in and on plaster, ink, wallboard, textiles, paper, adhesives, soaps, synthetic detergents, cutting oils, polymeric materials, embalming fluids, oil paints and latex paints to prevent the attack of various fungal organisms and the subsequent economic loss due to the degradation of such products by microorganisms. Also, the compounds can be distributed in textiles, cellulosic materials or in grain or can be employed in the impregnation of wood and lumber to preserve and protect such products from the attack of the organisms of rot, mold and decay.

The exact concentration of the toxicant to be employed in the treating compositions is not critical and may vary considerably provided the required dosage of the effective agent is supplied in the ink, adhesive, soap, cutting oil, polymeric material, paint, textile, paper, wood or growth medium or upon plant foliage. The concentration of toxicant in liquid compositions generally is from about 0.0001 to 50 percent by weight. Concentrations up to percent by weight are oftentimes conveniently employed, particularly in concentrate compositions. In dusts, the concentrations of the toxicant can be from about 0.1 to 95 percent by weight. In compositions to be employed as concentrates, the toxicants can be present in a concentration of from 5 to 98 percent by weight. For use as a foliar spray or in seed treatment, it is often convenient to apply the com-- pounds as wettable powders.

In a representative operation, each of the compounds 3-chloro-p-dithiino(2,3-c)pyridazine; 6,7-dichloro-pdithiino(2,3-b)pyrazine-2,3-dicarbonitrile; bis-pdithiino(2,3-b:2,3-e)pyridine-2,3,7,8,10- pentacarbonitrile; 5,8-dichloro-p-dithiino(2,3- d)pyridazine-Z,3-dicarbonitrile and 6,7-dichloro-pdithiino( 2,3 -b )-pyridine-2,3 ,8-tricarbonitrile, when employed as the sole toxicant in an aqueous composition at a concentration of 400 parts by weight per million parts of the ultimate composition, was found to give substantially complete kill and control of the causative organism of downey mildew.

In a further operation, each of (l) 4,5-dibromo-pdithiino( 2,3-e)(2, 1 ,3 )benzothiadiazole-7,8- dicarbonitrile and (2) a mixture of 6,8-dichloro-pdithiino( 2,3-b )pyridine-2,3 ,7-tricarbonitrile and 5 ,7- dichloro-p-dithiino(2,3-c)pyridine-2,3,8-tricarbonitrile were also found to give substantially complete kill and control of the causative organism of downey mildew when said mixture was employed, as the sole toxicant, in an aqueous composition at a concentration of 400 parts by weight per million parts of the ultimate composition.

In other representative operations, each of the compounds 6,7-dichloro-p-dithiino(2,3-b)pyridine-2,3,8- tricarbonitrile; p-dithiino(2,3-b)pyrazine-2,3- dicarbonitrile; bis-p-dithiino( 2,3-bz2 ,3 -e )pyridine- 2,3 ,7,8 l O-pentacarbonitrile; 6,7 ,8 ,9-tetrachloro-pdithiino( 2,3-b )quinoxaline-2,3-dicarbonitrile; bis-pdithiino(2,3-b:2,3'-e)pyrazine-2,3,7,8-

5,8-dichloro-p-dithiino(2,3-d)pyridazine-2,3-

dicarbonitrile; 6,7-p-dithiino(2,3'-b)pyrazine-2,3- dicarbonitrile, when employed as the sole toxicant in an aqueous composition at a concentration of 400 parts by weight per million parts of the ultimate composition was found to give substantially complete kill. and control of the causative organism of rice blast.

To a similar operation, each of (l) a mixture of 6,8- dichloro-p-dithiino(2,3-b)pyridine-2,3,7- tricarbonitrile and 5,7-dichloro-p-dithiino(2,3-

' c)pyridine-2,3,8-tricarbonitrile and (2) 4,5-dibrmo-p- 6,7-dichloro-p-dithiino( 2,3-b )pyrazine-2,3-

dicarbonitrile; 5,6,-dichloro-p-dithiino(2,3- d)pyridazine-Z,3dicarb0nitrile and 6,7-dichloro-pdithiino(2,3 b)pyridine-2,3,8-tricarbonitrile was found to give substantially complete kill and control of the causative organism of tomato late blight, when said compound was employed as the sole toxicant in an aqueous dispersion at a concentration of 400 parts by weight per million parts of the ultimate dispersion.

In an additional operation, each of the compounds p-dithiino(2,3-b)pyrazine-2,3-dicarbonitrile; 3-chlorop-dithiino(2,3-c)pyridazine-6,7-dicarbonitrile; 6,7- dichloro-p-dithiino(2,3-b)pyrazine-2,3-dicarbonitrile; bis-p-dithiino(2,3-b:2',3'-e)pyrazine-2,3,7,8- tetracarbonitrile; 6,7-dichloro-p-dithiino(2,3- b)pyridine-2,3,8-tricarbonitrile and bis-p-dithiino(2,3- c:2',3 '-g)( 2, l ,3 )-benzothiadiazole-5 ,6,9,10- tetracarbonitrile, when employed as the sole toxicant in a nutrient agar at a concentration of about 500 parts by weight of the compound per million parts of agar, is found to give 100 percent kill and control of the organisms Staphylococcus aureus, Trichophyton mentagrophytes, Candida albicans, Bacillus subtilis, Pullularia pullulans, Mycobacterium phlei, Aspergillns terreus, Candida pelliculosa, Rhizopus nigricans, Ceratocystis ips and Cephaloascus fragans.

Preparation of Starting Materials The disodium-cisl ,2 dicyano-l ,2-ethylenedithiolate employed as a starting material in the present invention is a well-known compound and can be prepared by the method taught in Meuterties inorganic Synthesis Volume X, page l I, wherein sodium cyanide is reacted with carbon disulfide and dimethylformamide followed by dimerization of the reaction product.

The chloro N-heterocyclic aromatic compounds employed as starting materials can be prepared by the method taught in US. Pat. No. 3,420,833 wherein the unchlorinated compound is subjected to vapor phase chlorination at temperatures of from about 400 to about 700 C. The chlorinated benzothiadiazole can be prepared by asimilar procedure.

The tetrabromobenzothiadiazole employed as a starting material is a known compound and can be prepared by the melt phase bromination of benzothiadiazol.

The 5 ,6-dibromo-(2,1,3)-benzothiadiazole employed as a starting material is a known compound andcan be prepared by the method taught in J. Heterocyclic Chemistry 7, 629 (1970) wherein 4,5-dibromo-ophenylene diamine is reacted with thionylaniline under reflux conditions in the presence of toluene.

What is claimed is:

l. The compound which is bis-p-dithiino(2,3-e:2,3 g)(2, l ,3 )benzothiadiazole-S ,6,9, l O-tetracarbonitrile corresponding to the formula CN AFN I cl 

1. THE COMPOUND WHICH IS BIS-P-DITHIINO(2,3-E:2'',3''G)(2,1,3)BENZOTHIADIAZOLE-5,6,9,10 -TETRACARBONITRILE CORRESPONDING TO THE FORMULA 